Cosmetic and pharmaceutical preparations containing photostable UV filters

ABSTRACT

4,4-Diarylbutadienes of the formula I,                    
     where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or a mixture thereof, and where the variables independently of one another have the following meanings: R 1  and R 2  are hydrogen, C 1 -C 20 -alkyl, C 2 -C 10 -alkenyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl, C 1 -C 12 -alkoxy, C 1 -C 20 -alkoxycarbonyl, C 1 -C 12 -alkylamino, C 1 -C 12 -dialkylamino, aryl, hetaryl, unsubstituted or substituted, substituents which confer solubility in water and are selected from the group consisting of carboxylate, sulfonate, or ammonium residues; R 3  is COOR 5 , CONR 5 R 6 ; R 4  is COOR 6 , CONR 5 R 6 ; R 5  and R 6  are hydrogen, C 1 -C 20 -alkyl, C 2 -C 10 -alkenyl, C 3 -C 10 -cycloalkyl, C 7 -C 10 -bicycloalkyl, C 3 -C 10 -cycloalkenyl, C 7 -C 10 -bicycloalkenyl, aryl, hetaryl, unsubstituted or substituted; n is 1 to 3; and R 3  and R 4  are not COOCH 3  when R 1  and R 2  are hydrogen, are used as photostable UV filters in cosmetic and pharmaceutical preparations to protect the human skin or human hair from the sun&#39;s rays, alone or together with compounds which absorb in the UV region and are known per se for cosmetic and pharmaceutical preparations.

This application is a divisional application of Ser. No. 09/133,173,filed Aug. 13, 1998 now U.S. Pat. No. 6,238,649.

The invention relates to the use of 4,4-diarylbutadienes as photostableUV filters in cosmetic and pharmaceutical preparations for protectingthe human epidermis or human hair from UV radiation, specifically in therange from 320 to 400 nm.

The sunscreens employed in cosmetic and pharmaceutical preparations havethe task of preventing, or at least diminishing the consequences of, theharmful effects of sunlight on the human skin. However, these sunscreensalso serve to protect other ingredients from decomposition or breakdownby UV radiation. The intention in hair cosmetic formulations is toreduce damage to the keratin fibers by UV rays.

The sunlight reaching the surface of the earth contains UV-B radiation(280 to 320 nm) and UV-A radiation (>320 nm), which are directlyadjacent to the visible light region. The effect on the human skin ismanifested, particularly with UV-B radiation, by sunburn. Accordingly,the industry supplies a relatively large number of substances whichabsorb UV-B radiation and thus prevent sunburn.

Dermatological investigations have now shown that UV-A radiation is alsoperfectly able to cause skin damage and allergies by, for example,damaging the keratin or elastin. This reduces the elasticity and waterstorage capacity of the skin, ie. the skin becomes less supple and tendsto form wrinkles. The noticeably high incidence of skin cancer inregions where the sun's radiation is strong shows that damage to thegenetic information in the cells is evidently also caused by sunlight,specifically by UV-A radiation. All these findings therefore make itappear necessary to develop efficient filter substances for the UV-Aregion.

There is a growing demand for sunscreens for cosmetic and pharmaceuticalpreparations which can be used in particular as UV-A filters and whoseabsorption maxima ought therefore to be in the range from about 320 to380 nm. In order to achieve the required effect by using the minimumamount, sunscreens of this type ought additionally to have a highspecific extinction. Sunscreens for cosmetic products must also meet alarge number of other requirements, for example good solubility incosmetic oils, high stability of the emulsions produced with them,toxicological acceptability, and slight intrinsic odor and littleintrinsic color.

Another requirement which sunscreens must meet is adequatephotostability. However, this is only inadequately ensured, if at all,with UV-A-absorbing sunscreens hitherto available.

French Patent No. 2 440 933 describes4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane as UV-A filter. It isproposed to combine this specific UV-A filter, which is sold by GIVAUDANunder the name “PARSOL 1789”, with various UV-B filters in order toabsorb all UV rays with a wavelength from 280 to 380 nm.

However, this UV-A filter does not have sufficient photochemicalstability, when it is used alone or in combination with UV-B filters, toensure sustained protection of the skin during lengthy sunbathing, whichmeans that repeated applications at regular and short intervals arerequired if effective protection of the skin from all UV rays isdesired.

For this reason, EP-A-0 514 491 discloses the stabilization ofinsufficiently photostable UV-A filters by adding2-cyano-3,3-diphenylacrylic esters which themselves act as filters inthe UV-B region.

It has furthermore been proposed in EP-A-0 251 398 to combinechromophores absorbing UV-A radiation and UV-B radiation into onemolecule by using a linker. This has the disadvantage that a freecombination of UV-A and UV-B filters in the cosmetic preparation is nolonger possible, and that difficulties in the chemical linkage of thechromophores allow only certain combinations.

U.S. Pat. No. 4,950,467 describes the use of 2,4-pentadienoic acidderivatives as UV absorbers in cosmetic products. Themonoaryl-substituted compounds which are mentioned as preferred in thispatent likewise have the disadvantage that their photostability isinsufficient.

It is an object of the present invention to propose sunscreens forcosmetic and pharmaceutical purposes which absorb in the UV-A regionwith high extinction, are photostable, have a slight intrinsic color,ie. a sharp band structure, and are soluble in oil or water depending onthe substituent.

We have found that this object is achieved by the use of4,4-diarylbutadienes of the formula I

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings:

R¹ and R² hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-cycloalkenyl, C₁-C₁₂-alkoxy, C₁-C₂₀-alkoxycarbonyl,C₁-C₁₂-alkylamino, C₁-C₁₂-dialkylamino, aryl, hetaryl, unsubstituted orsubstituted,

substituents which confer solubility in water and are selected from thegroup consisting of carboxylate, sulfonate or ammonium residues;

R³ hydrogen, COOR⁵, COR⁵, CONR⁵R⁶, CN, O═S(—R⁵)═O, O═S(—OR⁵)═O,R⁷O—P(—OR⁸)═O,

C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl, C₇-C₁₀-bicycloalkyl,C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl, hetaryl, unsubstitutedor substituted;

R⁴ COOR⁶, COR⁶, CONR⁵R⁶, CN, O═S(—R⁶)═O, O═S(—OR⁶)═O, R⁷O—P(—OR⁸)═O

C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl, C₇-C₁₀-bicycloalkyl,C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl, hetaryl, unsubstitutedor substituted;

R⁵ to R⁸ hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,hetaryl, unsubstituted or substituted;

n from 1 to 3;

where the variables R³ to R⁸ may, in each case together with the carbonatoms to which they are bonded, together form a 5- or 6-membered ringwhich may be further fused,

as photostable UV filters in cosmetic and pharmaceutical compositionsfor protecting the human skin or human hair from the sun's rays, aloneor together with compounds which absorb in the UV region and are knownper se for cosmetic and pharmaceutical preparations.

Alkyl radicals R¹ to R⁸ which may be mentioned are branched orunbranched C₁-C₂₀-alkyl chains, preferably methyl, ethyl, n-propyl,1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl or n-eicosyl.

Alkenyl radicals R¹ to R⁸ which may be mentioned are branched orunbranched C₂-C₁₀-alkenyl chains, preferably vinyl, propenyl,isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl,2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl,2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.

Cycloalkyl radicals which may be mentioned for R¹ to R⁸ are preferablyunsubstituted or alkyl-substituted C₃-C₁₀-cycloalkyl rings such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl,1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-2-butylcyclopropyl,1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl,cyclononyl or cyclodecyl.

Cycloalkenyl radicals which may be mentioned for R¹ to R⁸ are preferablyunsubstituted or alkyl-substituted C₃-C₁₀-cycloalkenyl rings with one ormore double bonds such as cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl,1,4-cyclohexadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl,1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.

The cycloalkenyl and cycloalkyl radicals may be unsubstituted orsubstituted by one or more, eg. 1 to 3, radicals such as halogen, eg.fluorine, chlorine or bromine, cyano, nitro, amino, C₁-C₄-alkylamino,C₁-C₄-dialkylamino, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy or otherradicals, or contain 1 to 3 heteroatoms such as sulfur, nitrogen, whosefree valencies can be saturated by hydrogen or C₁-C₄-alkyl, or oxygen inthe ring.

Bicycloalkyl or bicycloalkenyl radicals which may be mentioned for R³ toR⁸ are saturated or unsaturated C₇-C₁₀ bicyclic ring systems, inparticular bicyclic terpenes such as pinane, pinene, bornane or camphorderivatives, or adamantane.

Suitable alkoxy radicals for R¹ to R² are those having 1 to 12 carbonatoms, preferably having 1 to 8 carbon atoms.

Examples which may be mentioned are:

methoxy- ethoxy- isopropoxy- n-propoxy- 1-methylpropoxy- n-butoxy-n-pentoxy- 2-methylpropoxy- 3-methylbutoxy- 1,1-dimethylpropoxy-2,2-dimethylpropoxy- hexoxy- 1-methyl-1-ethylpropoxy- heptoxy- octoxy-2-ethylhexoxy-

Examples of alkoxycarbonyl radicals for R¹ and R² are those containingthe abovementioned alkoxy radicals or radicals derived from higheralcohols, eg. having up to 20 carbon atoms, such as iso-C₁₅ alcohol.

Suitable mono- or dialkylamino radicals for R¹ and R² are thosecontaining alkyl radicals having 1 to 12 carbon atoms, such as methyl,n-propyl, n-butyl, 2-methylpropyl, 1,1-dimethylpropyl, hexyl, heptyl,2-ethylhexyl, isopropyl, 1-methylpropyl, n-pentyl, 3-methylbutyl,2,2-dimethylpropyl, 1-methyl-1-ethylpropyl and octyl.

Aryl means aromatic rings or ring systems having 6 to 18 carbon atoms inthe ring system, for example phenyl or naphthyl, each of which may beunsubstituted or substituted by one or more radicals such as halogen,eg. fluorine, chlorine or bromine, cyano, nitro, amino,C₁-C₄-alkylamino, C₁-C₄-dialkylamino, hydroxyl, C₁-C₄-alkyl,C₁-C₄-alkoxy or other radicals. Unsubstituted or substituted phenyl,methoxyphenyl and naphthyl are preferred.

Hetaryl radicals are advantageously simple or fused aromatic ringsystems having one or more heteroaromatic 3- to 7-membered rings.Heteroatoms which may be present in the ring or ring system are one ormore nitrogen, sulfur and/or oxygen atoms.

Hydrophilic radicals, ie. those making it possible for compounds of theformula I to dissolve in water, for R¹ and R² are, for example, carboxyland sulfo radicals and, in particular, their salts with anyphysiologically tolerated cations, such as the alkali metal salts orsuch as the trialkylammonium salts, such as tri(hydroxyalkyl)ammoniumsalts or the 2-hydroxymethyl-2-propylammonium salts. Also suitable areammonium radicals, especially alkylammonium radicals, with anyphysiologically tolerated anions.

Preferred compounds of the formula I are those where

R¹ and R² are, independently of one another, hydrogen, C₁-C₁₂-alkyl,C₁-C₈-alkoxy, C₁-C₁₂-alkylamino, C₁-C₁₂-dialkylamino,

substituents which confer solubility in water and are selected from thegroup consisting of carboxylate, sulfonate or ammonium residues;

R³ is hydrogen, COOR⁵, COR⁵, CONR⁵R⁶, CN, C₁-C₁₂-alkyl,C₃-C₆-cycloalkyl, C₇-C₁₀-bicycloalkyl, phenyl, naphthyl, thienyl,unsubstituted or substituted;

R⁴ is COOR⁶, COR⁶, CONR⁵R⁶, CN, C₁-C₁₂-alkyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, phenyl, naphthyl, thienyl, unsubstituted orsubstituted;

R⁵ and R⁶ are, independently of one another, hydrogen, C₁-C₁₂-alkyl,C₃-C₆-cycloalkyl, C₇-C₁₀-bicycloalkyl, phenyl, naphthyl, unsubstitutedor substituted;

n is from 1 to 3.

C₁-C₁₂-Alkyl radicals which are particularly preferred for R¹ to R⁶ aremethyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 2-ethylhexyl.

Cycloalkyl radicals particularly preferred for R³ to R⁶ are branched orunbranched cyclopentyl and cyclohexyl.

Suitable and particularly preferred alkyl radicals for mono- ordialkylamino for R¹ and R² are methyl, ethyl, n-propyl, n-butyl,2-methylpropyl, 1,1-dimethylpropyl and 2-ethylhexyl.

Bicycloalkyl radicals particularly preferred for R³ to R⁶ are camphorderivatives.

The substituents R¹ and R² may each be bonded to the aromatic ring inthe ortho, meta and/or para position. In the case of disubstitutedaromatic rings (n=2), R¹ and R² can be in the ortho/para or meta/paraposition. Preferred compounds of the formula I where n=1 are those inwhich R¹ is identical to R² and both radicals are in the para position.

It is furthermore particularly preferred to use compounds of the formulaI where R³ or R⁴ is not H, CN, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, aryl,hetaryl, unsubstituted or substituted, when respectively R⁴ or R³ isCOOR⁵ or COOR⁶.

Very particularly preferred compounds of the formula I are those where

R¹ and R² are independently of one another hydrogen, C₁-C₁₂-alkyl,C₁-C₈-alkoxy, substituents which confer solubility in water and areselected from the group consisting of carboxylate, sulfonate or ammoniumresidues;

R³ is hydrogen, COOR⁵, COR⁵, CONR⁵R⁶, CN, C₃-C₆-cycloalkyl,C₇-C₁₀-bicycloalkyl;

R⁴ is COOR⁶, COR⁶, CONR⁵R⁶, CN, C₃-C₆-cycloalkyl, C₇-C₁₀-bicycloalkyl,

where R³ or R⁴ is not COOR⁵ or COOR⁶ when R⁴ is CN or R³ is hydrogen orCN;

R⁵ and R⁶ are independently of one another hydrogen, C₁-C₁₂-alkyl,C₃-C₆-cycloalkyl, C₇-C₁₀-bicycloalkyl, phenyl, naphthyl, unsubstitutedor substituted;

n is from 1 to 3.

Furthermore, compounds of the formula I (n=1) with particularlyphotostable properties are those where the substituents R¹ to R⁴ arepresent in the combination stated in Table 1:

TABLE 1

R¹ R² Position R³ R⁴ H H H COR⁶ H H H CONR⁵R⁶ H H H CN H H COOR⁵ COOR⁶ HH COOR⁵ COR⁶ H H COR⁵ COR⁶ H H CONR⁵R⁶ COOR⁶ H H CONR⁵R⁶ COR⁶ H HCONR⁵R⁶ CONR⁵R⁶ H H CN COR⁶ H H CN CONR⁵R⁶ H H CN CN C₁—C₈-AlkoxyC₁—C₈-Alkoxy para H COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho H COR⁶C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta H COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para HCONR⁵R⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho H CONR⁵R⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy meta H CONR⁵R⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para H CNC₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho H CN C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta H CNC₁—C₈-Alkoxy C₁—C₈-Alkoxy para COOR⁵ COOR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxyortho COOR⁵ COOR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta COOR⁵ COOR⁶C₁—C₈-Alkoxy C₁—C₈-Alkoxy para COOR⁵ COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxyortho COOR⁵ COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta COOR⁵ COR⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy para COR⁵ COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho COR⁵ COR⁶C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta COR⁵ COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy paraCONR⁵R⁶ COOR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho CONR⁵R⁶ COOR⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy meta CONR⁵R⁶ COOR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para CONR⁵R⁶COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho CONR⁵R⁶ COR⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy meta CONR⁵R⁶ COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para CONR⁵R⁶CONR⁵R⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho CONR⁵R⁶ CONR⁵R⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy meta CONR⁵R⁶ CONR⁵R⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para CN COR⁶C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho CN COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy metaCN COR⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy para CN CONR⁵R⁶ C₁—C₈-AlkoxyC₁—C₈-Alkoxy ortho CN CONR⁵R⁶ C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta CN CONR⁵R⁶C₁—C₈-Alkoxy C₁—C₈-Alkoxy para CN CN C₁—C₈-Alkoxy C₁—C₈-Alkoxy ortho CNCN C₁—C₈-Alkoxy C₁—C₈-Alkoxy meta CN CN C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy paraH COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy ortho H COR⁶ C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy meta H COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para H CONR⁵R⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy ortho H CONR⁵R⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxymeta H CONR⁵R⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para H CN C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy ortho H CN C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta H CNC₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para COOR⁵ COOR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxyortho COOR⁵ COOR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta COOR⁵ COOR⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para COOR⁵ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxyortho COOR⁵ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta COOR⁵ COR⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para COR⁵ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxyortho COR⁵ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta COR⁵ COR⁶ C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy para CONR⁵R⁶ COOR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy orthoCONR⁵R⁶ COOR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta CONR⁵R⁶ COOR⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para CONR⁵R⁶ COR⁶ C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy ortho CONR⁵R⁶ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy metaCONR⁵R⁶ COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para CONR⁵R⁶ CONR⁵R⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy ortho CONR⁵R⁶ CONR⁵R⁶ C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy meta CONR⁵R⁶ CONR⁵R⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para CNCOR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy ortho CN COR⁶ C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy meta CN COR⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para CN CONR⁵R⁶C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy ortho CN CONR⁵R⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxymeta CN CONR⁵R⁶ C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy para CN CN C₁—C₁₂-AlkoxyC₁—C₁₂-Alkoxy ortho CN CN C₁—C₁₂-Alkoxy C₁—C₁₂-Alkoxy meta CN CNCarboxylate Carboxylate para H COR⁶ Carboxylate Carboxylate ortho H COR⁶Carboxylate Carboxylate meta H COR⁶ Carboxylate Carboxylate para HCONR⁵R⁶ Carboxylate Carboxylate ortho H CONR⁵R⁶ Carboxylate Carboxylatemeta H CONR⁵R⁶ Carboxylate Carboxylate para H CN Carboxylate Carboxylateortho H CN Carboxylate Carboxylate meta H CN Carboxylate Carboxylatepara COOR⁵ COOR⁶ Carboxylate Carboxylate ortho COOR⁵ COOR⁶ CarboxylateCarboxylate meta COOR⁵ COOR⁶ Carboxylate Carboxylate para COOR⁵ COR⁶Carboxylate Carboxylate ortho COOR⁵ COR⁶ Carboxylate Carboxylate metaCOOR⁵ COR⁶ Carboxylate Carboxylate para COR⁵ COR⁶ CarboxylateCarboxylate ortho COR⁵ COR⁶ Carboxylate Carboxylate meta COR⁵ COR⁶Carboxylate Carboxylate para CONR⁵R⁶ COOR⁶ Carboxylate Carboxylate orthoCONR⁵R⁶ COOR⁶ Carboxylate Carboxylate meta CONR⁵R⁶ COOR⁶ CarboxylateCarboxylate para CONR⁵R⁶ COR⁶ Carboxylate Carboxylate ortho CONR⁵R⁶ COR⁶Carboxylate Carboxylate meta CONR⁵R⁶ COR⁶ Carboxylate Carboxylate paraCONR⁵R⁶ CONR⁵R⁶ Carboxylate Carboxylate ortho CONR⁵R⁶ CONR⁵R⁶Carboxylate Carboxylate meta CONR⁵R⁶ CONR⁵R⁶ Carboxylate Carboxylatepara CN COR⁶ Carboxylate Carboxylate ortho CN COR⁶ CarboxylateCarboxylate meta CN COR⁶ Carboxylate Carboxylate para CN CONR⁵R⁶Carboxylate Carboxylate ortho CN CONR⁵R⁶ Carboxylate Carboxylate meta CNCONR⁵R⁶ Carboxylate Carboxylate para CN CN Carboxylate Carboxylate orthoCN CN Carboxylate Carboxylate meta CN CN Sulfonate Sulfonate para H COR⁶Sulfonate Sulfonate ortho H COR⁶ Sulfonate Sulfonate meta H COR⁶Sulfonate Sulfonate para H CONR⁵R⁶ Sulfonate Sulfonate ortho H CONR⁵R⁶Sulfonate Sulfonate meta H CONR⁵R⁶ Sulfonate Sulfonate para H CNSulfonate Sulfonate ortho H CN Sulfonate Sulfonate meta H CN SulfonateSulfonate para COOR⁵ COOR⁶ Sulfonate Sulfonate ortho COOR⁵ COOR⁶Sulfonate Sulfonate meta COOR⁵ COOR⁶ Sulfonate Sulfonate para COOR⁵ COR⁶Sulfonate Sulfonate ortho COOR⁵ COR⁶ Sulfonate Sulfonate meta COOR⁵ COR⁶Sulfonate Sulfonate para COR⁵ COR⁶ Sulfonate Sulfonate ortho COR⁵ COR⁶Sulfonate Sulfonate meta COR⁵ COR⁶ Sulfonate Sulfonate para CONR⁵R⁶COOR⁶ Sulfonate Sulfonate ortho CONR⁵R⁶ COOR⁶ Sulfonate Sulfonate metaCONR⁵R⁶ COOR⁶ Sulfonate Sulfonate para CONR⁵R⁶ COR⁶ Sulfonate Sulfonateortho CONR⁵R⁶ COR⁶ Sulfonate Sulfonate meta CONR⁵R⁶ COR⁶ SulfonateSulfonate para CONR⁵R⁶ CONR⁵R⁶ Sulfonate Sulfonate ortho CONR⁵R⁶ CONR⁵R⁶Sulfonate Sulfonate meta CONR⁵R⁶ CONR⁵R⁶ Sulfonate Sulfonate para CNCOR⁶ Sulfonate Sulfonate ortho CN COR⁶ Sulfonate Sulfonate meta CN COR⁶Sulfonate Sulfonate para CN CONR⁵R⁶ Sulfonate Sulfonate ortho CN CONR⁵R⁶Sulfonate Sulfonate meta CN CONR⁵R⁶ Sulfonate Sulfonate para CN CNSulfonate Sulfonate ortho CN CN Sulfonate Sulfonate meta CN CN AmmoniumAmmonium para H COR⁶ Ammonium Ammonium ortho H COR⁶ Ammonium Ammoniummeta H COR⁶ Ammonium Ammonium para H CONR⁵R⁶ Ammonium Ammonium ortho HCONR⁵R⁶ Ammonium Ammonium meta H CONR⁵R⁶ Ammonium Ammonium para H CNAmmonium Ammonium ortho H CN Ammonium Ammonium meta H CN AmmoniumAmmonium para COOR⁵ COOR⁶ Ammonium Ammonium ortho COOR⁵ COOR⁶ AmmoniumAmmonium meta COOR⁵ COOR⁶ Ammonium Ammonium para COOR⁵ COR⁶ AmmoniumAmmonium ortho COOR⁵ COR⁶ Ammonium Ammonium meta COOR⁵ COR⁶ AmmoniumAmmonium para COR⁵ COR⁶ Ammonium Ammonium ortho COR⁵ COR⁶ AmmoniumAmmonium meta COR⁵ COR⁶ Ammonium Ammonium para CONR⁵R⁶ COOR⁶ AmmoniumAmmonium ortho CONR⁵R⁶ COOR⁶ Ammonium Ammonium meta CONR⁵R⁶ COOR⁶Ammonium Ammonium para CONR⁵R⁶ COR⁶ Ammonium Ammonium ortho CONR⁵R⁶ COR⁶Ammonium Ammonium meta CONR⁵R⁶ COR⁶ Ammonium Ammonium para CONR⁵R⁶CONR⁵R⁶ Ammonium Ammonium ortho CONR⁵R⁶ CONR⁵R⁶ Ammonium Ammonium metaCONR⁵R⁶ CONR⁵R⁶ Ammonium Ammonium para CN COR⁶ Ammonium Ammonium orthoCN COR⁶ Ammonium Ammonium meta CN COR⁶ Ammonium Ammonium para CN CONR⁵R⁶Ammonium Ammonium ortho CN CONR⁵R⁶ Ammonium Ammonium meta CN CONR⁵R⁶Ammonium Ammonium para CN CN Ammonium Ammonium ortho CN CN AmmoniumAmmonium meta CN CN

Likewise very particularly preferred is the use of those compounds ofthe formula I where

R¹ and R² are independently of one another hydrogen, C₁-C₁₂-alkyl,C₁-C₈-alkoxy,

substituents which confer solubility in water and are selected from thegroup consisting of carboxylate, sulfonate or ammonium residues;

R³ is COOR⁵, COR⁵, CONR⁵R⁶;

R⁴ is COOR⁶, COR⁶, CONR⁵R⁶;

R⁵ and R⁶ are independently of one another hydrogen, C₁-C₁₂-alkyl,C₃-C₆-cycloalkyl, C₇-C₁₀-bicycloalkyl, phenyl, naphthyl, unsubstitutedor substituted;

n is from 1 to 3,

since these compounds are particularly photostable and, at the sametime, colorless.

The invention also relates to 4,4-diarylbutadienes of the formula Ia,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings:

R¹ and R² hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-cycloalkenyl, C₁-C₁₂-alkoxy, C₁-C₂₀-alkoxycarbonyl,C₁-C₁₂-alkylamino, C₁-C₁₂-dialkylamino, aryl, hetaryl, unsubstituted orsubstituted,

substituents which confer solubility in water and are selected from thegroup consisting of carboxylate, sulfonate or ammonium residues;

R³ COOR⁵, CONR⁵R⁶;

R⁴ COOR⁶, CONR⁵R⁶;

R⁵ and R⁶ hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,hetaryl, unsubstituted or substituted;

n 1 to 3,

where R³ and R⁴ may not be COOCH₃ when R¹ and R² are hydrogen.

Preferred 4,4-diarylbutadienes are those of the formula Ib,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings:

R¹ and R² hydrogen, C₁-C₂₀-alkyl, C₁-C₁₂-alkoxy, C₁-C₂₀-alkoxycarbonyl;

R³ COOR⁵, CONR⁵R⁶;

R⁴ COOR⁶, CONR⁵R⁶;

R⁵ and R⁶ hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,hetaryl, unsubstituted or substituted;

where R³ and R⁴ may not be COOCH₃ when R¹ and R² are hydrogen.

Particularly preferred 4,4-diarylbutadienes are those of the formula Ic,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture htereof, and where the variables independently of one anotherhave the following meanings:

R¹ and R² hydrogen, C₁-C₂₀-alkyl, C₁-C₁₂-alkoxy, C₁-C₂₀-alkoxycarbonyl;

R³ COOR⁵, CONR⁵R⁶;

R⁴ COOR⁶, CONR⁵R⁶;

R⁵ and R⁶ hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,hetaryl, unsubstituted or substituted;

where R³ and R⁴ may not be COOCH₃ when R¹ and R² are hydrogen.

The more accurate definition of the substituents R¹ to R⁶ of compoundsIa to Ic corresponds to the description of compound I previously givenin the introduction.

The compounds of the formula I to be used according to the invention canbe prepared by condensation in accordance with the equation

where R¹ to R⁴ have the meanings stated in claim 1.

The abovementioned condensation can be either base- or acid-catalyzed.Suitable catalysts are:

tertiary amines such as, for example, pyridine, morpholine,triethylamine, triethanolamine;

seconday amines such as, for example, piperidine, dimethylamine,diethylamine;

NH₃, NaNH₂, KNH₂, NH₄OAc;

basic alumina, basic ion exchangers;

Na₂CO₃, K₂CO₃;

acid catalysts such as, for example, glacial acetic acid, formic acid,propionic acid;

HCl, H₂SO₄, HNO₃;

acid ion exchangers.

The amount of the catalysts is in general 0.1 to 50 mol %, preferably0.5 to 20 mol %, of the amount of aldehyde employed.

The temperatures preferably employed are from 20 to 150° C., inparticular 30 to 100° C., particularly preferably from 40 to 80° C. Nospecial conditions regarding the pressure are necessary; the reaction isgenerally carried out under atmospheric pressure.

Solvents which can be employed are alcohols such as, for example,methanol, ethanol or isopropanol; aromatic compounds such as, forexample, toluene or xylene; hydrocarbons, for example heptane or hexane;chlorinated hydrocarbons such as, for example, chloroform ordichloromethane; miglyol, tetrahydrofuran. However, the reaction canalso be carried out without solvent.

For example, reaction of β-phenylcinnamaldehyde with diethyl malonate inthe presence of piperidine as catalyst affords compound 1 in Tab. 2.

It is also possible to prepare longer-chain esters starting from methylor ethyl esters, such as, for example, compound 1 in Table 2, bytransesterification reactions in the presence of a basic catalyst.

Catalysts suitable for the transesterification are:

basic alkali metal and alkaline earth metal salts, preferably thosewhich are soluble neither in the precursors nor in the products andwhich can easily be removed after the end of the reaction, particularlypreferably: sodium, potassium or calcium carbonate or sodiumbicarbonate;

alkaline earth metal oxides, preferably calcium or magnesium oxide and

basic zeolites.

The amount of the catalysts is generally from 1 to 80 mol %, preferably5 to 50 mol %, of the amount of ester employed.

The amount of alcohol employed must be at least equimolar with theamount of initial ester employed, for example compound 1 in Table 2.Amounts of from 200 to 500 mol % of the alcohol are preferably employed.

The methanol or ethanol which is formed is removed by distillation.

The temperatures preferably employed are from 50 to 250° C., inparticular 60 to 150° C. No special conditions regarding the pressureare necessary; the reaction is generally carried out under atmosphericpressure.

Solvents which can be employed are inert high-boiling compounds such asxylenes, but also toluene or mixtures of the alcohols employed withliquid, short-chain alkanes such as hexane and heptane. It is preferredto use no solvent except the alcohol employed.

The transesterification can be carried out either batchwise orcontinuously. In the continuous procedure, the reactants are preferablypassed over a fixed bed of an insoluble base.

In the case where R³≠R⁴, the compounds of the formula I according to theinvention can, in principle, be in the form of their various geometricisomers, i.e. with a diene system having the Z,Z; Z,E; E,Z and/or E,Econfiguration. The preferred cosmetic sunscreens are the all-E and/orall-Z isomers, very particularly preferably the all-E isomers.

If R³=R⁴, the C—C double bond between C-3 and C-4 (adjacent to thediaryl system) can have the E and/or Z configuration, preferably the Zconfiguration.

The present invention also relates to cosmetic and pharmaceuticalpreparations which comprise from 0.1 to 10% by weight, preferably 1 to7% by weight, based on the total amount of the cosmetic andpharmaceutical preparation, of one or more of the compounds of theformula I together with compounds known per se for cosmetic andpharmaceutical preparations and absorbing in the UV-A and UV-B regionsas sunscreens, generally employing the compounds of the formula I in asmaller amount than the UV-B-absorbing compounds.

The sunscreen-containing cosmetic and pharmaceutical preparations are,as a rule, based on a carrier which contains at least one oil phase.However, preparations with an exclusively aqueous basis are alsopossible on use of compounds having hydrophilic substituents.Accordingly, oils, oil-in-water and water-in-oil emulsions, creams andpastes, protective lipstick bases or non-greasy gels are suitable.

Sunscreen products of these types can accordingly be in liquid, pasty orsolid form, for example as water-in-oil creams, oil-in-water creams andlotions, aerosol foam creams, gels, oils, grease sticks, dustingpowders, sprays or hydroalcoholic lotions.

Examples of conventional cosmetic oil components are liquid paraffin,glyceryl stearate, isopropyl myristate, diisopropyl adipate,cetylstearyl 2-ethylhexanoate, hydrogenated polyisobutene, petrolatum,caprylic acid/capric acid triglycerides, microcrystalline wax, lanolinand stearic acid.

Conventional cosmetic ancillary substances which may be suitable asadditives are, for example, coemulsifiers, fats and waxes, stabilizers,thickeners, biogenic active substances, film formers, fragrances, dyes,pearlescent agents, preservatives, pigments, electrolytes (eg. magnesiumsulfate) and pH regulators. Suitable and preferred coemulsifiers areknown water in oil (W/O) as well as oil in water (O/W) emulsifiers suchas polyglycerol esters, sorbitan esters or partially esterifiedglycerides. Typical examples of fats are glycerides; waxes which may bementioned are, inter alia, beeswax, paraffin wax or microwaxes, possiblycombined with hydrophilic waxes. Stabilizers which can be employed aremetal salts of fatty acids such as magnesium, aluminum and/or zincstearate. Examples of suitable thickeners are crosslinked polyacrylicacids and their derivatives, polysaccharides, in particular xanthan gum,guar—guar, agar—agar, alginates and Tyloses, carboxymethylcellulose andhydroxyethylcellulose, also fatty alcohols, monoglycerides and fattyacids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone.Examples of biogenic active substances are plant extracts, proteinhydrolysates and vitamin complexes. Examples of film formers which arein use are hydrocolloids such as chitosan, microcrystalline chitosan orquaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinylacetate copolymers, polymers of the acrylic acid series, quaternarycellulose derivatives and similar compounds. Examples of suitablepreservatives are formaldehyde solution, p-hydroxybenzoate or sorbicacid. Examples of suitable pearlescent agents are glycol distearicesters such as ethylene glycol distearate, but also fatty acids andfatty acid monoglycol esters. Dyes which can be used are the substancessuitable and approved for cosmetic purposes, as tabulated, for example,in the publication “Kosmetische Färbemittel” of the Farbstoffkomissionder Deutschen Forschungsgemeinschaft, published in Verlag Chemie,Weinheim, 1984. These dyes are normally employed in a concentration offrom 0.001 to 0.1% of the total weight of the mixture.

The total content of ancillary substances and additives can be from 1 to80, preferably 6 to 40, % by weight, and the nonaqueous content (“activesubstance”) can be from 20 to 80, preferably 30 to 70, % by weight,based on the compositions. The compositions can be produced in a mannerknown per se, ie. for example by hot, cold, hot—hot/cold or PhaseInversion Temperature (PIT) emulsification. This is a purely mechanicalprocess; no chemical reaction takes place.

Finally, it is also possible to use other substances which absorb in theUV region and are known per se as long as they are stable in thecomplete system of the combination of UV filters to be used according tothe invention.

Most of the sunscreens in the cosmetic and pharmaceutical preparationsused for protecting the human epidermis consist of compounds whichabsorb UV light in the UV-B region, ie. in the region from 280 to 320nm. The content of UV-A absorbers to be used according to the inventionis, for example, from 10 to 90%, preferably 20 to 50%, of the totalweight of UV-B and UV-A absorbing substances.

Any V-A and UV-B filter substances are suitable as UV filter substanceswhich are used in combination with the compounds of the formula I to beused according to the invention. Examples which may be mentioned are:

CAS No. No. Substance (= acid)  1 4-Aminobenzoic acid 150-13-0  23-(4-Trimethylammonio)benzylidenebornan-2-one 52793-97-2 methyl sulfate 3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9 (homosalate)  42-Hydroxy-4-methoxybenzophenone 131-57-7 (oxybenzone)  52-Phenylbenzimidazole-5-sulfonic acid and its 27503-81-7 potassium,sodium and triethanolamine salts  63,3′-(1,4-Phenylenedimethine)bis(7,7- 90457-82-2dimethyl-2-oxobicyclo[2.2.1]heptane-1-methane- sulfonic acid) and itssalts  7 Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9  82-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3  9 2-Ethylhexylsalicylate 118-60-5 10 Isoamyl 4-methoxycinnamate 71617-10-2 112-Ethylhexyl 4-methoxycinnamate 5466-77-3 122-Hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6(sulisobenzone) and the sodium salt 133-(4-Methylbenzylidene)bornan-2-one 36861-47-9 143-Benzylidenebornan-2-one 15087-24-8 151-(4-Isopropylphenyl)-3-phenylpropane-1,3- 63250-25-9 dione 164-Isopropylbenzyl salicylate 94134-93-7 172,4,6-Tri(o-2-ethylhexoxycarbonyl- 88122-99-0 anilino)-1,3,5-triazine 183-(4-Imidazolyl)acrylic acid and its ethyl 104-98-3 ester 19 Ethyl2-cyano-3,3-diphenylacrylate 5232-99-5 20 2-Ethylhexyl2-cyano-3,3-diphenylacrylate 6197-30-4 21 Menthyl o-aminobenzoate or:134-09-8 5-methyl-2-(1-methylethyl)cyclohexyl 2-aminobenzoate 22Glyceryl p-aminobenzoate or: 136-44-7 4-aminobenzoic acid 1-glycerylester 23 2,2′-Dihydroxy-4-methoxybenzophenone 131-53-3 (dioxybenzone) 242-Hydroxy-4-methoxy-4′-methylbenzophenone 1641-17-4 (mexenone) 25Triethanolamine salicylate 2174-16-5 26 Dimethoxyphenylglyoxylic acidor: 4732-70-1 sodium 3,4-dimethoxyphenylglyoxylate 273-(4-Sulfobenzylidene)bornan-2-one and its 56039-58-8 salts 284-tert-Butyl-4′-methoxydibenzoylmethane 70356-09-1 292,2′,4,4′-Tetrahydroxybenzophenone 131-55-5

Finally, mention may also be made of micronized pigments such astitanium dioxide and zinc oxide.

To protect human hair from UV rays, the sunscreens of the formula Iaccording to the invention can be incorporated into shampoos, lotions,gels, hair sprays, aerosol foam creams or emulsions in concentrations offrom 0.1 to 10% by weight, preferably 1 to 7% by weight. The particularformulations can be used inter alia for washing, coloring and settingthe hair.

The compounds to be used according to the invention as a rule have aparticularly high absorbance in the region of UV-A radiation with asharp band structure. They are furthermore readily soluble in cosmeticoils and can easily be incorporated into cosmetic formulations.Emulsions prepared using the compounds I show particularly highstability, the compounds I themselves show high photostability, and thepreparations produced with I have a pleasant skin feel.

The UV filter action of the compounds of the formula I according to theinvention can also be utilized for stabilizing active and ancillarysubstances in cosmetic and pharmaceutical formulations.

The invention also relates to the compounds of the formula I for use asmedicine and to pharmaceutical compositions for preventive treatment ofinflammations and allergies of the skin, and for preventing certaintypes of skin cancer, which comprise an effective amount of at least onecompound of the formula I as active substance.

The pharmaceutical compositions according to the invention can beadministered orally or topically. For oral administration, thepharmaceutical composition is in the form of, inter alia, pastilles,gelatine capsules, coated tablets, syrup, solution, emulsion orsuspension. The pharmaceutical compositions are used topically forexample as ointment, cream, gel, spray, solution or lotion.

EXAMPLES

I. Preparation

Example 1

Method for Preparing Compound No. 1 in Table 2

0.1 mol of β-phenylcinnamaldehyde and 0.1 mol of diethyl malonate weredissolved in 100 ml of methanol, 1 ml each of piperidine and glacialacetic acid was added, and the mixture was refluxed for 5 h. It is thendiluted with water and cooled to 0° C., during which the final productcrystallized out. The crystals were filtered off and dried to give 33 g(90% of theory) of compound 1 in Table 2 as colorless crystals.Purity: >99% (GC).

Compounds 2 and 3 and 8 to 15 in Table 2 are prepared as in Example 1.

Compounds 18 to 20 were prepared as in Example 1 by reacting diethylmalonate with the corresponding methyl-, tert-butyl- ormethoxy-substituted β-phenylcinnamaldehydes.

Example 2

Compounds 4 to 7 in Table 2 were prepared by transesterifiation of thecompound from Example 1 with the appropriate alcohols in the presence ofsodium carbonate as catalyst. The liberated ethanol was distilled off,and the required products 4 to 7, which resulted as oil, were purifiedby distillation.

Example 3

Method for Preparing Compound No. 17 in Table 2

0.1 mol of camphor in 40 ml of xylene are mixed with 0.1 mol of KOH andheated to reflux. Then a solution of 0.105 mol of β-phenylcinnamaldehydein xylene is slowly added dropwise over the course of 6 h. After coolingto room temperature, water is added, and the organic phase is washedtwice with water and then dried over sodium sulfate. The oily residueafter removal of the solvent is crystallized from methanol/water. 22 g(64%) of colorless crystals of compound 17 in Table 2 are obtained.Purity 99% (HPLC, isomer mixture).

Compound 16 in Table 2 is prepared by reacting β-phenylcinnamaldehydewith pinacolone as in Example 2.

TABLE 2

No.

R¹ R² n λmax (nm) E¹ ₁ 1)

H H 1 334 802 2)

H H 1 334 775 3)

H H 1 334 684 4)

H H 1 334 681 5)

H H 1 333 655 6)

H H 1 334 602 7)

H H 1 334 580 8)

H H 1 344 977 9)

H H 1 342 806 10)

H H 1 336 693 11)

H H 1 350 806 12)

H H 1 342 525 13)

H H 1 340 776 14)

H H 1 338 802 15)

H H 1 332 814 16)

H H 1 334 960 17)

H H 1 338 901 18)

¹⁾ ¹⁾ 1 364 672 19)

²⁾ ²⁾ 1 346 643 20)

³⁾ ³⁾ 2 338 699 ¹⁾ R¹═R² = methoxy (substituted in the para position) ²⁾R¹═R² = tert-butyl (substituted in the para position) ³⁾ R¹═R² = methyl(substituted in the ortho and para position)

The compounds in Tables 3 and 4 can be prepared in a similar way or asdescribed in the general part.

TABLE 3

Posi- No. R⁵═R⁶ R¹ R² n tion 1) n-Propyl H H 1 — 2) 2,2-Dimethylpropyl HH 1 — 3) n-Pentyl H H 1 — 4) 3-Methylbutyl H H 1 — 5) 2-Methylbutyl H H1 — 6) 1-Methylbutyl H H 1 — 7) n-Heptyl H H 1 — 8) n-Octyl H H 1 — 9)Methyl Methyl Methyl 1 para 10) Ethyl Methyl Methyl 1 para 11) n-PropylMethyl Methyl 2 para 12) iso-Propyl Methyl Methyl 1 para 13) n-ButylMethyl Methyl 1 para 14) 2-Methylpropyl Methyl Methyl 1 para 15)1-Methylpropyl Methyl Methyl 1 para 16) 2,2-Dimethylpropyl Methyl Methyl1 para 17) n-Pentyl Methyl Methyl 1 para 18) 3-Methylbutyl Methyl Methyl1 para 19) 2-Methylbutyl Methyl Methyl 1 para 20) 1-Methylbutyl MethylMethyl 2 para 21) n-Hexyl Methyl Methyl 1 para 22) n-Heptyl MethylMethyl 1 para 23) n-Octyl Methyl Methyl 1 para 24) 2-Ethylhexyl MethylMethyl 1 para 25) Methyl Ethyl Ethyl 1 para 26) Ethyl Ethyl Ethyl 1 para27) n-Propyl Ethyl Ethyl 1 para 28) iso-Propyl Ethyl Ethyl 1 para 29)n-Butyl Ethyl Ethyl 1 para 30) 2-Methylpropyl Ethyl Ethyl 1 para 31)1-Methylpropyl Ethyl Ethyl 1 para 32) 2,2-Dimethylpropyl Ethyl Ethyl 1para 33) n-Pentyl Ethyl Ethyl 1 para 34) 3-Methylbutyl Ethyl Ethyl 1para 35) 2-Methylbutyl Ethyl Ethyl 1 para 36) 1-Methylbutyl Ethyl Ethyl1 para 37) n-Hexyl Ethyl Ethyl 1 para 38) n-Heptyl Ethyl Ethyl 1 para39) n-Octyl Ethyl Ethyl 1 para 40) 2-Ethylhexyl Ethyl Ethyl 1 para 41)Methyl n-Propyl n-Propyl 1 para 42) Ethyl n-Propyl n-Propyl 1 para 43)n-Propyl n-Propyl n-Propyl 1 para 44) iso-Propyl n-Propyl n-Propyl 1para 45) n-Butyl n-Propyl n-Propyl 1 para 46) 2-Methylpropyl n-Propyln-Propyl 1 para 47) 1-Methylpropyl n-Propyl n-Propyl 1 para 48)2,2-Dimethylpropyl n-Propyl n-Propyl 1 para 49) n-Pentyl n-Propyln-Propyl 1 para 50) 3-Methylbutyl n-Propyl n-Propyl 1 para 51)2-Methylbutyl n-Propyl n-Propyl 1 para 52) 1-Methylbutyl n-Propyln-Propyl 1 para 53) n-Hexyl n-Propyl n-Propyl 1 para 54) n-Heptyln-Propyl n-Propyl 1 para 55) n-Octyl n-Propyl n-Propyl 1 para 56)2-Ethylhexyl n-Propyl n-Propyl 1 para 57) Methyl i-Propyl i-Propyl 1para 58) Ethyl i-Propyl i-Propyl 1 para 59) n-Propyl i-Propyl i-Propyl 1para 60) iso-Propyl i-Propyl i-Propyl 1 para 61) n-Butyl i-Propyli-Propyl 1 para 62) 2-Methylpropyl i-Propyl i-Propyl 1 para 63)1-Methylpropyl i-Propyl i-Propyl 1 para 64) 2,2-Dimethylpropyl i-Propyli-Propyl 1 para 65) n-Pentyl i-Propyl i-Propyl 1 para 66) 3-Methylbutyli-Propyl i-Propyl 1 para 67) 2-Methylbutyl i-Propyl i-Propyl 1 para 68)1-Methylbutyl i-Propyl i-Propyl 1 para 69) n-Hexyl i-Propyl i-Propyl 1para 70) n-Heptyl i-Propyl i-Propyl 1 para 71) n-Octyl i-Propyl i-Propyl1 para 72) 2-Ethylhexyl i-Propyl i-Propyl 1 para 73) Methyl n-Butyln-Butyl 1 para 74) Ethyl n-Butyl n-Butyl 1 para 75) n-Propyl n-Butyln-Butyl 1 para 76) iso-Propyl n-Butyl n-Butyl 1 para 77) n-Butyl n-Butyln-Butyl 1 para 78) 2-Methylpropyl n-Butyl n-Butyl 1 para 79)1-Methylpropyl n-Butyl n-Butyl 1 para 80) 2,2-Dimethylpropyl n-Butyln-Butyl 1 para 81) n-Pentyl n-Butyl n-Butyl 1 para 82) 3-Methylbutyln-Butyl n-Butyl 1 para 83) 2-Methylbutyl n-Butyl n-Butyl 1 para 84)1-Methylbutyl n-Butyl n-Butyl 1 para 85) n-Hexyl n-Butyl n-Butyl 1 para86) n-Heptyl n-Butyl n-Butyl 1 para 87) n-Octyl n-Butyl n-Butyl 1 para88) 2-Ethylhexyl n-Butyl n-Butyl 1 para 89) Methyl 1-Methylpropyl1-Methylpropyl 1 para 90) Ethyl 1-Methylpropyl 1-Methylpropyl 1 para 91)n-Propyl 1-Methylpropyl 1-Methylpropyl 1 para 92) iso-Propyl1-Methylpropyl 1-Methylpropyl 1 para 93) n-Butyl 1-Methylpropyl1-Methylpropyl 1 para 94) 2-Methylpropyl 1-Methylpropyl 1-Methylpropyl 1para 95) 1-Methylpropyl 1-Methylpropyl 1-Methylpropyl 1 para 96)2,2-Dimethylpropyl 1-Methylpropyl 1-Methylpropyl 1 para 97) n-Pentyl1-Methylpropyl 1-Methylpropyl 1 para 98) 3-Methylbutyl 1-Methylpropyl1-Methylpropyl 1 para 99) 2-Methylbutyl 1-Methylpropyl 1-Methylpropyl 1para 100) 1-Methylbutyl 1-Methylpropyl 1-Methylpropyl 1 para 101)n-Hexyl 1-Methylpropyl 1-Methylpropyl 1 para 102) n-Heptyl1-Methylpropyl 1-Methylpropyl 1 para 103) n-Octyl 1-Methylpropyl1-Methylpropyl 1 para 104) 2-Ethylhexyl 1-Methylpropyl 1-Methylpropyl 1para 105) Methyl 2-Methylpropyl 2-Methylpropyl 1 para 106) Ethyl2-Methylpropyl 2-Methylpropyl 1 para 107) n-Propyl 2-Methylpropyl2-Methylpropyl 1 para 108) iso-Propyl 2-Methylpropyl 2-Methylpropyl 1para 109) n-Butyl 2-Methylpropyl 2-Methylpropyl 1 para 110)2-Methylpropyl 2-Methylpropyl 2-Methylpropyl 1 para 111) 1-Methylpropyl2-Methylpropyl 2-Methylpropyl 1 para 112) 2,2-Dimethylpropyl2-Methylpropyl 2-Methylpropyl 1 para 113) n-Pentyl 2-Methylpropyl2-Methylpropyl 1 para 114) 3-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1para 115) 2-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1 para 116)1-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1 para 117) n-Hexyl2-Methylpropyl 2-Methylpropyl 1 para 118) n-Heptyl 2-Methylpropyl2-Methylpropyl 1 para 119) n-Octyl 2-Methylpropyl 2-Methylpropyl 1 para120) 2-Ethylhexyl 2-Methylpropyl 2-Methylpropyl 1 para 121) Methyln-Pentyl n-Pentyl 1 para 122) Ethyl n-Pentyl n-Pentyl 1 para 123)n-Propyl n-Pentyl n-Pentyl 1 para 124) iso-Propyl n-Pentyl n-Pentyl 1para 125) n-Butyl n-Pentyl n-Pentyl 1 para 126) 2-Methylpropyl n-Pentyln-Pentyl 1 para 127) 1-Methylpropyl n-Pentyl n-Pentyl 1 para 128)2,2-Dimethylpropyl n-Pentyl n-Pentyl 1 para 129) n-Pentyl n-Pentyln-Pentyl 1 para 130) 3-Methylbutyl n-Pentyl n-Pentyl 1 para 131)2-Methylbutyl n-Pentyl n-Pentyl 1 para 132) 1-Methylbutyl n-Pentyln-Pentyl 1 para 133) n-Hexyl n-Pentyl n-Pentyl 1 para 134) n-Heptyln-Pentyl n-Pentyl 1 para 135) n-Octyl n-Pentyl n-Pentyl 1 para 136)2-Ethylhexyl n-Pentyl n-Pentyl 1 para 137) Methyl n-Hexyl n-Hexyl 1 para138) Ethyl n-Hexyl n-Hexyl 1 para 139) n-Propyl n-Hexyl n-Hexyl 1 para140) iso-Propyl n-Hexyl n-Hexyl 1 para 141) n-Butyl n-Hexyl n-Hexyl 1para 142) 2-Methylpropyl n-Hexyl n-Hexyl 1 para 143) 1-Methylpropyln-Hexyl n-Hexyl 1 para 144) 2,2-Dimethylpropyl n-Hexyl n-Hexyl 1 para145) n-Pentyl n-Hexyl n-Hexyl 1 para 146) 3-Methylbutyl n-Hexyl n-Hexyl1 para 147) 2-Methylbutyl n-Hexyl n-Hexyl 1 para 148) 1-Methylbutyln-Hexyl n-Hexyl 1 para 149) n-Hexyl n-Hexyl n-Hexyl 1 para 150) n-Heptyln-Hexyl n-Hexyl 1 para 151) n-Octyl n-Hexyl n-Hexyl 1 para 152)2-Ethylhexyl n-Hexyl n-Hexyl 1 para 153) Methyl Methoxy Methoxy 1 para154) Ethyl Methoxy Methoxy 1 para 155) n-Propyl Methoxy Methoxy 1 para156) iso-Propyl Methoxy Methoxy 1 para 157) n-Butyl Methoxy Methoxy 1para 158) 2-Methylpropyl Methoxy Methoxy 1 para 159) 1-MethylpropylMethoxy Methoxy 1 para 160) 2,2-Dimethylpropyl Methoxy Methoxy 1 para161) n-Pentyl Methoxy Methoxy 1 para 162) 3-Methylbutyl Methoxy Methoxy1 para 163) 2-Methylbutyl Methoxy Methoxy 1 para 164) 1-MethylbutylMethoxy Methoxy 1 para 165) n-Hexyl Methoxy Methoxy 1 para 166) n-HeptylMethoxy Methoxy 1 para 167) n-Octyl Methoxy Methoxy 1 para 168)2-Ethylhexyl Methoxy Methoxy 1 para 169) Methyl Ethoxy Ethoxy 1 para170) Ethyl Ethoxy Ethoxy 1 para 171) n-Propyl Ethoxy Ethoxy 1 para 172)iso-Propyl Ethoxy Ethoxy 1 para 173) n-Butyl Ethoxy Ethoxy 1 para 174)2-Methylpropyl Ethoxy Ethoxy 1 para 175) 1-Methylpropyl Ethoxy Ethoxy 1para 176) 2,2-Dimethylpropyl Ethoxy Ethoxy 1 para 177) n-Pentyl EthoxyEthoxy 1 para 178) 3-Methylbutyl Ethoxy Ethoxy 1 para 179) 2-MethylbutylEthoxy Ethoxy 1 para 180) 1-Methylbutyl Ethoxy Ethoxy 1 para 181)n-Hexyl Ethoxy Ethoxy 1 para 182) n-Heptyl Ethoxy Ethoxy 1 para 183)n-Octyl Ethoxy Ethoxy 1 para 184) 2-Ethylhexyl Ethoxy Ethoxy 1 para 185)Methyl Methyl Methyl 2 o/p*) 186) n-Propyl Methyl Methyl 2 187)iso-Propyl Methyl Methyl 2 188) n-Butyl Methyl Methyl 2 189)2-Methylpropyl Methyl Methyl 2 190) 1-Methylpropyl Methyl Methyl 2 191)2,2-Dimethylpropyl Methyl Methyl 2 o/p*) 192) n-Pentyl Methyl Methyl 2o/p*) 193) 3-Methylbutyl Methyl Methyl 2 o/p*) 194) 2-Methylbutyl MethylMethyl 2 o/p*) 195) 1-Methylbutyl Methyl Methyl 2 o/p*) 196) n-HexylMethyl Methyl 2 o/p*) 197) n-Heptyl Methyl Methyl 2 o/p*) 198) n-OctylMethyl Methyl 2 o/p*) 199) 2-Ethylhexyl Methyl Methyl 2 o/p*) 200)Methyl Ethyl Ethyl 2 o/p*) 201) Ethyl Ethyl Ethyl 2 o/p*) 202) n-PropylEthyl Ethyl 2 o/p*) 203) iso-Propyl Ethyl Ethyl 2 o/p*) 204) n-ButylEthyl Ethyl 2 o/p*) 205) 2-Methylpropyl Ethyl Ethyl 2 o/p*) 206)1-Methylpropyl Ethyl Ethyl 2 o/p*) 207) 2,2-Dimethylpropyl Ethyl Ethyl 2o/p*) 208) n-Pentyl Ethyl Ethyl 2 o/p*) 209) 3-Methylbutyl Ethyl Ethyl 2o/p*) 210) 2-Methylbutyl Ethyl Ethyl 2 o/p*) 211) 1-Methylbutyl EthylEthyl 2 o/p*) 212) n-Hexyl Ethyl Ethyl 2 o/p*) 213) n-Heptyl Ethyl Ethyl2 o/p*) 214) n-Octyl Ethyl Ethyl 2 o/p*) 215) 2-Ethylhexyl Ethyl Ethyl 2o/p*) 216) Methyl n-Propyl n-Propyl 2 o/p*) 217) Ethyl n-Propyl n-Propyl2 o/p*) 218) n-Propyl n-Propyl n-Propyl 2 o/p*) 219) iso-Propyl n-Propyln-Propyl 2 o/p*) 220) n-Butyl n-Propyl n-Propyl 2 o/p*) 221)2-Methylpropyl n-Propyl n-Propyl 2 o/p*) 222) 1-Methylpropyl n-Propyln-Propyl 2 o/p*) 223) 2,2-Dimethylpropyl n-Propyl n-Propyl 2 o/p*) 224)n-Pentyl n-Propyl n-Propyl 2 o/p*) 225) 3-Methylbutyl n-Propyl n-Propyl2 o/p*) 226) 2-Methylbutyl n-Propyl n-Propyl 2 o/p*) 227) 1-Methylbutyln-Propyl n-Propyl 2 o/p*) 228) n-Hexyl n-Propyl n-Propyl 2 o/p*) 229)n-Heptyl n-Propyl n-Propyl 2 o/p*) 230) n-Octyl n-Propyl n-Propyl 2o/p*) 231) 2-Ethylhexyl n-Propyl n-Propyl 2 o/p*) 232) Methyl i-Propyli-Propyl 2 o/p*) 233) Ethyl i-Propyl i-Propyl 2 o/p*) 234) n-Propyli-Propyl i-Propyl 2 o/p*) 235) iso-Propyl i-Propyl i-Propyl 2 o/p*) 236)n-Butyl i-Propyl i-Propyl 2 o/p*) 237) 2-Methylpropyl i-Propyl i-Propyl2 o/p*) 238) 1-Methylpropyl i-Propyl i-Propyl 2 o/p*) 239)2,2-Dimethylpropyl i-Propyl i-Propyl 2 o/p*) 240) n-Pentyl i-Propyli-Propyl 2 o/p*) 241) 3-Methylbutyl i-Propyl i-Propyl 2 o/p*) 242)2-Methylbutyl i-Propyl i-Propyl 2 o/p*) 243) 1-Methylbutyl i-Propyli-Propyl 2 o/p*) 244) n-Hexyl i-Propyl i-Propyl 2 o/p*) 245) n-Heptyli-Propyl i-Propyl 2 o/p*) 246) n-Octyl i-Propyl i-Propyl 2 o/p*) 247)2-Ethylhexyl i-Propyl i-Propyl 2 o/p*) 248) Methyl n-Butyl n-Butyl 2o/p*) 249) Ethyl n-Butyl n-Butyl 2 o/p*) 250) n-Propyl n-Butyl n-Butyl 2o/p*) 251) iso-Propyl n-Butyl n-Butyl 2 o/p*) 252) n-Butyl n-Butyln-Butyl 2 o/p*) 253) 2-Methylpropyl n-Butyl n-Butyl 2 o/p*) 254)1-Methylpropyl n-Butyl n-Butyl 2 o/p*) 255) 2,2-Dimethylpropyl n-Butyln-Butyl 2 o/p*) 256) n-Pentyl n-Butyl n-Butyl 2 o/p*) 257) 3-Methylbutyln-Butyl n-Butyl 2 o/p*) 258) 2-Methylbutyl n-Butyl n-Butyl 2 o/p*) 259)1-Methylbutyl n-Butyl n-Butyl 2 o/p*) 260) n-Hexyl n-Butyl n-Butyl 2o/p*) 261) n-Heptyl n-Butyl n-Butyl 2 o/p*) 262) n-Octyl n-Butyl n-Butyl2 o/p*) 263) 2-Ethylhexyl n-Butyl n-Butyl 2 o/p*) 264) Methyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 265) Ethyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 266) n-Propyl 1-Methylpropyl 1-Methylpropyl 2o/p*) 267) iso-Propyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 268) n-Butyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 269) 2-Methylpropyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 270) 1-Methylpropyl 1-Methylpropyl 1-Methylpropyl2 o/p*) 271) 2,2-Dimethylpropyl 1-Methylpropyl 1-Methylpropyl 2 o/p*)272) n-Pentyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 273) 3-Methylbutyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 274) 2-Methylbutyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 275) 1-Methylbutyl 1-Methylpropyl 1-Methylpropyl2 o/p*) 276) n-Hexyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 277) n-Heptyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 278) n-Octyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 279) 2-Ethylhexyl 1-Methylpropyl 1-Methylpropyl 2o/p*) 280) Methyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 281) Ethyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 282) n-Propyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 283) iso-Propyl 2-Methylpropyl 2-Methylpropyl 2o/p*) 284) n-Butyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 285)2-Methylpropyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 286) 1-Methylpropyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 287) 2,2-Dimethylpropyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 288) n-Pentyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 289) 3-Methylbutyl 2-Methylpropyl 2-Methylpropyl2 o/p*) 290) 2-Methylbutyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 291)1-Methylbutyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 292) n-Hexyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 293) n-Heptyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 294) n-Octyl 2-Methylpropyl 2-Methylpropyl 2o/p*) 295) 2-Ethylhexyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 296)Methyl n-Pentyl n-Pentyl 2 o/p*) 297) Ethyl n-Pentyl n-Pentyl 2 o/p*)298) n-Propyl n-Pentyl n-Pentyl 2 o/p*) 299) iso-Propyl n-Pentyln-Pentyl 2 o/p*) 300) n-Butyl n-Pentyl n-Pentyl 2 o/p*) 301)2-Methylpropyl n-Pentyl n-Pentyl 2 o/p*) 302) 1-Methylpropyl n-Pentyln-Pentyl 2 o/p*) 303) 2,2-Dimethylpropyl n-Pentyl n-Pentyl 2 o/p*) 304)n-Pentyl n-Pentyl n-Pentyl 2 o/p*) 305) 3-Methylbutyl n-Pentyl n-Pentyl2 o/p*) 306) 2-Methylbutyl n-Pentyl n-Pentyl 2 o/p*) 307) 1-Methylbutyln-Pentyl n-Pentyl 2 o/p*) 308) n-Hexyl n-Pentyl n-Pentyl 2 o/p*) 309)n-Heptyl n-Pentyl n-Pentyl 2 o/p*) 310) n-Octyl n-Pentyl n-Pentyl 2o/p*) 311) 2-Ethylhexyl n-Pentyl n-Pentyl 2 o/p*) 312) Methyl n-Hexyln-Hexyl 2 o/p*) 313) Ethyl n-Hexyl n-Hexyl 2 o/p*) 314) n-Propyl n-Hexyln-Hexyl 2 o/p*) 315) iso-Propyl n-Hexyl n-Hexyl 2 o/p*) 316) n-Butyln-Hexyl n-Hexyl 2 o/p*) 317) 2-Methylpropyl n-Hexyl n-Hexyl 2 o/p*) 318)1-Methylpropyl n-Hexyl n-Hexyl 2 o/p*) 319) 2,2-Dimethylpropyl n-Hexyln-Hexyl 2 o/p*) 320) n-Pentyl n-Hexyl n-Hexyl 2 o/p*) 321) 3-Methylbutyln-Hexyl n-Hexyl 2 o/p*) 322) 2-Methylbutyl n-Hexyl n-Hexyl 2 o/p*) 323)1-Methylbutyl n-Hexyl n-Hexyl 2 o/p*) 324) n-Hexyl n-Hexyl n-Hexyl 2o/p*) 325) n-Heptyl n-Hexyl n-Hexyl 2 o/p*) 326) n-Octyl n-Hexyl n-Hexyl2 o/p*) 327) 2-Ethylhexyl n-Hexyl n-Hexyl 2 o/p*) 328) Methyl MethoxyMethoxy 2 o/p*) 329) Ethyl Methoxy Methoxy 2 o/p*) 330) n-Propyl MethoxyMethoxy 2 o/p*) 331) iso-Propyl Methoxy Methoxy 2 o/p*) 332) n-ButylMethoxy Methoxy 2 o/p*) 333) 2-Methylpropyl Methoxy Methoxy 2 o/p*) 334)1-Methylpropyl Methoxy Methoxy 2 o/p*) 335) 2,2-Dimethylpropyl MethoxyMethoxy 2 o/p*) 336) n-Pentyl Methoxy Methoxy 2 o/p*) 337) 3-MethylbutylMethoxy Methoxy 2 o/p*) 338) 2-Methylbutyl Methoxy Methoxy 2 o/p*) 339)1-Methylbutyl Methoxy Methoxy 2 o/p*) 340) n-Hexyl Methoxy Methoxy 2o/p*) 341) n-Heptyl Methoxy Methoxy 2 o/p*) 342) n-Octyl Methoxy Methoxy2 o/p*) 343) 2-Ethylhexyl Methoxy Methoxy 2 o/p*) 344) Methyl EthoxyEthoxy 2 o/p*) 345) Ethyl Ethoxy Ethoxy 2 o/p*) 346) n-Propyl EthoxyEthoxy 2 o/p*) 347) iso-Propyl Ethoxy Ethoxy 2 o/p*) 348) n-Butyl EthoxyEthoxy 2 o/p*) 349) 2-Methylpropyl Ethoxy Ethoxy 2 o/p*) 350)1-Methylpropyl Ethoxy Ethoxy 2 o/p*) 351) 2,2-Dimethylpropyl EthoxyEthoxy 2 o/p*) 352) n-Pentyl Ethoxy Ethoxy 2 o/p*) 353) 3-MethylbutylEthoxy Ethoxy 2 o/p*) 354) 2-Methylbutyl Ethoxy Ethoxy 2 o/p*) 355)1-Methylbutyl Ethoxy Ethoxy 2 o/p*) 356) n-Hexyl Ethoxy Ethoxy 2 o/p*)357) n-Heptyl Ethoxy Ethoxy 2 o/p*) 358) n-Octyl Ethoxy Ethoxy 2 o/p*)359) 2-Ethylhexyl Ethoxy Ethoxy 2 o/p*) *) o/p represents ortho- andpara-substituted

TABLE 4

Posi- No. R⁵ = R⁶ R¹ R² n tion 1) Methyl H H 1 — 2) Ethyl H H 1 — 3)n-Propyl H H 1 — 4) iso-Propyl H H 1 — 5) n-Butyl H H 1 — 6)2-Methylpropyl H H 1 — 7) 1-Methylpropyl H H 1 — 8) 2,2-Dimethylpropyl HH 1 — 9) n-Pentyl H H 1 — 10) 3-Methylbutyl H H 1 — 11) 2-Methylbutyl HH 1 — 12) 1-Methylbutyl H H 1 — 13) n-Hexyl H H 1 — 14) n-Heptyl H H 1 —15) n-Octyl H H 1 — 16) 2-Ethylhexyl H H 1 — 17) Methyl Methyl Methyl 1para 18) Ethyl Methyl Methyl 1 para 19) n-Propyl Methyl Methyl 1 para20) iso-Propyl Methyl Methyl 1 para 21) n-Butyl Methyl Methyl 1 para 22)2-Methylpropyl Methyl Methyl 1 para 23) 1-Methylpropyl Methyl Methyl 1para 24) 2,2-Dimethylpropyl Methyl Methyl 1 para 25) n-Pentyl MethylMethyl 1 para 26) 3-Methylbutyl Methyl Methyl 1 para 27) 2-MethylbutylMethyl Methyl 1 para 28) 1-Methylbutyl Methyl Methyl 1 para 29) n-HexylMethyl Methyl 1 para 30) n-Heptyl Methyl Methyl 1 para 31) n-OctylMethyl Methyl 1 para 32) 2-Ethylhexyl Methyl Methyl 1 para 33) MethylEthyl Ethyl 1 para 34) Ethyl Ethyl Ethyl 1 para 35) n-Propyl Ethyl Ethyl1 para 36) iso-Propyl Ethyl Ethyl 1 para 37) n-Butyl Ethyl Ethyl 1 para38) 2-Methylpropyl Ethyl Ethyl 1 para 39) 1-Methylpropyl Ethyl Ethyl 1para 40) 2,2-Dimethylpropyl Ethyl Ethyl 1 para 41) n-Pentyl Ethyl Ethyl1 para 42) 3-Methylbutyl Ethyl Ethyl 1 para 43) 2-Methylbutyl EthylEthyl 1 para 44) 1-Methylbutyl Ethyl Ethyl 1 para 45) n-Hexyl EthylEthyl 1 para 46) n-Heptyl Ethyl Ethyl 1 para 47) n-Octyl Ethyl Ethyl 1para 48) 2-Ethylhexyl Ethyl Ethyl 1 para 49) Methyl n-Propyl n-Propyl 1para 50) Ethyl n-Propyl n-Propyl 1 para 51) n-Propyl n-Propyl n-Propyl 1para 52) iso-Propyl n-Propyl n-Propyl 1 para 53) n-Butyl n-Propyln-Propyl 1 para 54) 2-Methylpropyl n-Propyl n-Propyl 1 para 55)1-Methylpropyl n-Propyl n-Propyl 1 para 56) 2,2-Dimethylpropyl n-Propyln-Propyl 1 para 57) n-Pentyl n-Propyl n-Propyl 1 para 58) 3-Methylbutyln-Propyl n-Propyl 1 para 59) 2-Methylbutyl n-Propyl n-Propyl 1 para 60)1-Methylbutyl n-Propyl n-Propyl 1 para 61) n-Hexyl n-Propyl n-Propyl 1para 62) n-Heptyl n-Propyl n-Propyl 1 para 63) n-Octyl n-Propyl n-Propyl1 para 64) 2-Ethylhexyl n-Propyl n-Propyl 1 para 65) Methyl i-Propyli-Propyl 1 para 66) Ethyl i-Propyl i-Propyl 1 para 67) n-Propyl i-Propyli-Propyl 1 para 68) iso-Propyl i-Propyl i-Propyl 1 para 69) n-Butyli-Propyl i-Propyl 1 para 70) 2-Methylpropyl i-Propyl i-Propyl 1 para 71)1-Methylpropyl i-Propyl i-Propyl 1 para 72) 2,2-Dimethylpropyl i-Propyli-Propyl 1 para 73) n-Pentyl i-Propyl i-Propyl 1 para 74) 3-Methylbutyli-Propyl i-Propyl 1 para 75) 2-Methylbutyl i-Propyl i-Propyl 1 para 76)1-Methylbutyl i-Propyl i-Propyl 1 para 77) n-Hexyl i-Propyl i-Propyl 1para 78) n-Heptyl i-Propyl i-Propyl 1 para 79) n-Octyl i-Propyl i-Propyl1 para 80) 2-Ethylhexyl i-Propyl i-Propyl 1 para 81) Methyl n-Butyln-Butyl 1 para 82) Ethyl n-Butyl n-Butyl 1 para 83) n-Propyl n-Butyln-Butyl 1 para 84) iso-Propyl n-Butyl n-Butyl 1 para 85) n-Butyl n-Butyln-Butyl 1 para 86) 2-Methylpropyl n-Butyl n-Butyl 1 para 87)1-Methylpropyl n-Butyl n-Butyl 1 para 88) 2,2-Dimethylpropyl n-Butyln-Butyl 1 para 89) n-Pentyl n-Butyl n-Butyl 1 para 90) 3-Methylbutyln-Butyl n-Butyl 1 para 91) 2-Methylbutyl n-Butyl n-Butyl 1 para 92)1-Methylbutyl n-Butyl n-Butyl 1 para 93) n-Hexyl n-Butyl n-Butyl 1 para94) n-Heptyl n-Butyl n-Butyl 1 para 95) n-Octyl n-Butyl n-Butyl 1 para96) 2-Ethylhexyl n-Butyl n-Butyl 1 para 97) Methyl 1-Methylpropyl1-Methylpropyl 1 para 98) Ethyl 1-Methylpropyl 1-Methylpropyl 1 para 99)n-Propyl 1-Methylpropyl 1-Methylpropyl 1 para 100) iso-Propyl1-Methylpropyl 1-Methylpropyl 1 para 101) n-Butyl 1-Methylpropyl1-Methylpropyl 1 para 102) 2-Methylpropyl 1-Methylpropyl 1-Methylpropyl1 para 103) 1-Methylpropyl 1-Methylpropyl 1-Methylpropyl 1 para 104)2,2-Dimethylpropyl 1-Methylpropyl 1-Methylpropyl 1 para 105) n-Pentyl1-Methylpropyl 1-Methylpropyl 1 para 106) 3-Methylbutyl 1-Methylpropyl1-Methylpropyl 1 para 107) 2-Methylbutyl 1-Methylpropyl 1-Methylpropyl 1para 108) 1-Methylbutyl 1-Methylpropyl 1-Methylpropyl 1 para 109)n-Hexyl 1-Methylpropyl 1-Methylpropyl 1 para 110) n-Heptyl1-Methylpropyl 1-Methylpropyl 1 para 111) n-Octyl 1-Methylpropyl1-Methylpropyl 1 para 112) 2-Ethylhexyl 1-Methylpropyl 1-Methylpropyl 1para 113) Methyl 2-Methylpropyl 2-Methylpropyl 1 para 114) Ethyl2-Methylpropyl 2-Methylpropyl 1 para 115) n-Propyl 2-Methylpropyl2-Methylpropyl 1 para 116) iso-Propyl 2-Methylpropyl 2-Methylpropyl 1para 117) n-Butyl 2-Methylpropyl 2-Methylpropyl 1 para 118)2-Methylpropyl 2-Methylpropyl 2-Methylpropyl 1 para 119) 1-Methylpropyl2-Methylpropyl 2-Methylpropyl 1 para 120) 2,2-Dimethylpropyl2-Methylpropyl 2-Methylpropyl 1 para 121) n-Pentyl 2-Methylpropyl2-Methylpropyl 1 para 122) 3-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1para 123) 2-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1 para 124)1-Methylbutyl 2-Methylpropyl 2-Methylpropyl 1 para 125) n-Hexyl2-Methylpropyl 2-Methylpropyl 1 para 126) n-Heptyl 2-Methylpropyl2-Methylpropyl 1 para 127) n-Octyl 2-Methylpropyl 2-Methylpropyl 1 para128) 2-Ethylhexyl 2-Methylpropyl 2-Methylpropyl 1 para 129) Methyln-Pentyl n-Pentyl 1 para 130) Ethyl n-Pentyl n-Pentyl 1 para 131)n-Propyl n-Pentyl n-Pentyl 1 para 132) iso-Propyl n-Pentyl n-Pentyl 1para 133) n-Butyl n-Pentyl n-Pentyl 1 para 134) 2-Methylpropyl n-Pentyln-Pentyl 1 para 135) 1-Methylpropyl n-Pentyl n-Pentyl 1 para 136)2,2-Dimethylpropyl n-Pentyl n-Pentyl 1 para 137) n-Pentyl n-Pentyln-Pentyl 1 para 138) 3-Methylbutyl n-Pentyl n-Pentyl 1 para 139)2-Methylbutyl n-Pentyl n-Pentyl 1 para 140) 1-Methylbutyl n-Pentyln-Pentyl 1 para 141) n-Hexyl n-Pentyl n-Pentyl 1 para 142) n-Heptyln-Pentyl n-Pentyl 1 para 143) n-Octyl n-Pentyl n-Pentyl 1 para 144)2-Ethylhexyl n-Pentyl n-Pentyl 1 para 145) Methyl n-Hexyl n-Hexyl 1 para146) Ethyl n-Hexyl n-Hexyl 1 para 147) n-Propyl n-Hexyl n-Hexyl 1 para148) iso-Propyl n-Hexyl n-Hexyl 1 para 149) n-Butyl n-Hexyl n-Hexyl 1para 150) 2-Methylpropyl n-Hexyl n-Hexyl 1 para 151) 1-Methylpropyln-Hexyl n-Hexyl 1 para 152) 2,2-Dimethylpropyl n-Hexyl n-Hexyl 1 para153) n-Pentyl n-Hexyl n-Hexyl 1 para 154) 3-Methylbutyl n-Hexyl n-Hexyl1 para 155) 2-Methylbutyl n-Hexyl n-Hexyl 1 para 156) 1-Methylbutyln-Hexyl n-Hexyl 1 para 157) n-Hexyl n-Hexyl n-Hexyl 1 para 158) n-Heptyln-Hexyl n-Hexyl 1 para 159) n-Octyl n-Hexyl n-Hexyl 1 para 160)2-Ethylhexyl n-Hexyl n-Hexyl 1 para 161) Methyl Methoxy Methoxy 1 para162) Ethyl Methoxy Methoxy 1 para 163) n-Propyl Methoxy Methoxy 1 para164) iso-Propyl Methoxy Methoxy 1 para 165) n-Butyl Methoxy Methoxy 1para 166) 2-Methylpropyl Methoxy Methoxy 1 para 167) 1-MethylpropylMethoxy Methoxy 1 para 168) 2,2-Dimethylpropyl Methoxy Methoxy 1 para169) n-Pentyl Methoxy Methoxy 1 para 170) 3-Methylbutyl Methoxy Methoxy1 para 171) 2-Methylbutyl Methoxy Methoxy 1 para 172) 1-MethylbutylMethoxy Methoxy 1 para 173) n-Hexyl Methoxy Methoxy 1 para 174) n-HeptylMethoxy Methoxy 1 para 175) n-Octyl Methoxy Methoxy 1 para 176)2-Ethylhexyl Methoxy Methoxy 1 para 177) Methyl Ethoxy Ethoxy 1 para178) Ethyl Ethoxy Ethoxy 1 para 179) n-Propyl Ethoxy Ethoxy 1 para 180)iso-Propyl Ethoxy Ethoxy 1 para 181) n-Butyl Ethoxy Ethoxy 1 para 182)2-Methylpropyl Ethoxy Ethoxy 1 para 183) 1-Methylpropyl Ethoxy Ethoxy 1para 184) 2,2-Dimethylpropyl Ethoxy Ethoxy 1 para 185) n-Pentyl EthoxyEthoxy 1 para 186) 3-Methylbutyl Ethoxy Ethoxy 1 para 187) 2-MethylbutylEthoxy Ethoxy 1 para 188) 1-Methylbutyl Ethoxy Ethoxy 1 para 189)n-Hexyl Ethoxy Ethoxy 1 para 190) n-Heptyl Ethoxy Ethoxy 1 para 191)n-Octyl Ethoxy Ethoxy 1 para 192) 2-Ethylhexyl Ethoxy Ethoxy 1 para 193)Methyl Methyl Methyl 2 o/p*) 194) Ethyl Methyl Methyl 2 o/p*) 195)n-Propyl Methyl Methyl 2 o/p*) 196) iso-Propyl Methyl Methyl 2 o/p*)197) n-Butyl Methyl Methyl 2 o/p*) 198) 2-Methylpropyl Methyl Methyl 2o/p*) 199) 1-Methylpropyl Methyl Methyl 2 o/p*) 200) 2,2-DimethylpropylMethyl Methyl 2 o/p*) 201) n-Pentyl Methyl Methyl 2 o/p*) 202)3-Methylbutyl Methyl Methyl 2 o/p*) 203) 2-Methylbutyl Methyl Methyl 2o/p*) 204) 1-Methylbutyl Methyl Methyl 2 o/p*) 205) n-Hexyl MethylMethyl 2 o/p*) 206) n-Heptyl Methyl Methyl 2 o/p*) 207) n-Octyl MethylMethyl 2 o/p*) 208) 2-Ethylhexyl Methyl Methyl 2 o/p*) 209) Methyl EthylEthyl 2 o/p*) 210) Ethyl Ethyl Ethyl 2 o/p*) 211) n-Propyl Ethyl Ethyl 2o/p*) 212) iso-Propyl Ethyl Ethyl 2 o/p*) 213) n-Butyl Ethyl Ethyl 2o/p*) 214) 2-Methylpropyl Ethyl Ethyl 2 o/p*) 215) 1-Methylpropyl EthylEthyl 2 o/p*) 216) 2,2-Dimethylpropyl Ethyl Ethyl 2 o/p*) 217) n-PentylEthyl Ethyl 2 o/p*) 218) 3-Methylbutyl Ethyl Ethyl 2 o/p*) 219)2-Methylbutyl Ethyl Ethyl 2 o/p*) 220) 1-Methylbutyl Ethyl Ethyl 2 o/p*)221) n-Hexyl Ethyl Ethyl 2 o/p*) 222) n-Heptyl Ethyl Ethyl 2 o/p*) 223)n-Octyl Ethyl Ethyl 2 o/p*) 224) 2-Ethylhexyl Ethyl Ethyl 2 o/p*) 225)Methyl n-Propyl n-Propyl 2 o/p*) 226) Ethyl n-Propyl n-Propyl 2 o/p*)227) n-Propyl n-Propyl n-Propyl 2 o/p*) 228) iso-Propyl n-Propyln-Propyl 2 o/p*) 229) n-Butyl n-Propyl n-Propyl 2 o/p*) 230)2-Methylpropyl n-Propyl n-Propyl 2 o/p*) 231) 1-Methylpropyl n-Propyln-Propyl 2 o/p*) 232) 2,2-Dimethylpropyl n-Propyl n-Propyl 2 o/p*) 233)n-Pentyl n-Propyl n-Propyl 2 o/p*) 234) 3-Methylbutyl n-Propyl n-Propyl2 o/p*) 235) 2-Methylbutyl n-Propyl n-Propyl 2 o/p*) 236) 1-Methylbutyln-Propyl n-Propyl 2 o/p*) 237) n-Hexyl n-Propyl n-Propyl 2 o/p*) 238)n-Heptyl n-Propyl n-Propyl 2 o/p*) 239) n-Octyl n-Propyl n-Propyl 2o/p*) 240) 2-Ethylhexyl n-Propyl n-Propyl 2 o/p*) 241) Methyl i-Propyli-Propyl 2 o/p*) 242) Ethyl i-Propyl i-Propyl 2 o/p*) 243) n-Propyli-Propyl i-Propyl 2 o/p*) 244) iso-Propyl i-Propyl i-Propyl 2 o/p*) 245)n-Butyl i-Propyl i-Propyl 2 o/p*) 246) 2-Methylpropyl i-Propyl i-Propyl2 o/p*) 247) 1-Methylpropyl i-Propyl i-Propyl 2 o/p*) 248)2,2-Dimethylpropyl i-Propyl i-Propyl 2 o/p*) 249) n-Pentyl i-Propyli-Propyl 2 o/p*) 250) 3-Methylbutyl i-Propyl i-Propyl 2 o/p*) 251)2-Methylbutyl i-Propyl i-Propyl 2 o/p*) 252) 1-Methylbutyl i-Propyli-Propyl 2 o/p*) 253) n-Hexyl i-Propyl i-Propyl 2 o/p*) 254) n-Heptyli-Propyl i-Propyl 2 o/p*) 255) n-Octyl i-Propyl i-Propyl 2 o/p*) 256)2-Ethylhexyl i-Propyl i-Propyl 2 o/p*) 257) Methyl n-Butyl n-Butyl 2o/p*) 258) Ethyl n-Butyl n-Butyl 2 o/p*) 259) n-Propyl n-Butyl n-Butyl 2o/p*) 260) iso-Propyl n-Butyl n-Butyl 2 o/p*) 261) n-Butyl n-Butyln-Butyl 2 o/p*) 262) 2-Methylpropyl n-Butyl n-Butyl 2 o/p*) 263)1-Methylpropyl n-Butyl n-Butyl 2 o/p*) 264) 2,2-Dimethylpropyl n-Butyln-Butyl 2 o/p*) 265) n-Pentyl n-Butyl n-Butyl 2 o/p*) 266) 3-Methylbutyln-Butyl n-Butyl 2 o/p*) 267) 2-Methylbutyl n-Butyl n-Butyl 2 o/p*) 268)1-Methylbutyl n-Butyl n-Butyl 2 o/p*) 269) n-Hexyl n-Butyl n-Butyl 2o/p*) 270) n-Heptyl n-Butyl n-Butyl 2 o/p*) 271) n-Octyl n-Butyl n-Butyl2 o/p*) 272) 2-Ethylhexyl n-Butyl n-Butyl 2 o/p*) 273) Methyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 274) Ethyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 275) n-Propyl 1-Methylpropyl 1-Methylpropyl 2o/p*) 276) iso-Propyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 277) n-Butyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 278) 2-Methylpropyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 279) 1-Methylpropyl 1-Methylpropyl 1-Methylpropyl2 o/p*) 280) 2,2-Dimethylpropyl 1-Methylpropyl 1-Methylpropyl 2 o/p*)281) n-Pentyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 282) 3-Methylbutyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 283) 2-Methylbutyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 284) 1-Methylbutyl 1-Methylpropyl 1-Methylpropyl2 o/p*) 285) n-Hexyl 1-Methylpropyl 1-Methylpropyl 2 o/p*) 286) n-Heptyl1-Methylpropyl 1-Methylpropyl 2 o/p*) 287) n-Octyl 1-Methylpropyl1-Methylpropyl 2 o/p*) 288) 2-Ethylhexyl 1-Methylpropyl 1-Methylpropyl 2o/p*) 289) Methyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 290) Ethyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 291) n-Propyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 292) iso-Propyl 2-Methylpropyl 2-Methylpropyl 2o/p*) 293) n-Butyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 294)2-Methylpropyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 295) 1-Methylpropyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 296) 2,2-Dimethylpropyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 297) n-Pentyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 298) 3-Methylbutyl 2-Methylpropyl 2-Methylpropyl2 o/p*) 299) 2-Methylbutyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 300)1-Methylbutyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 301) n-Hexyl2-Methylpropyl 2-Methylpropyl 2 o/p*) 302) n-Heptyl 2-Methylpropyl2-Methylpropyl 2 o/p*) 303) n-Octyl 2-Methylpropyl 2-Methylpropyl 2o/p*) 304) 2-Ethylhexyl 2-Methylpropyl 2-Methylpropyl 2 o/p*) 305)Methyl n-Pentyl n-Pentyl 2 o/p*) 306) Ethyl n-Pentyl n-Pentyl 2 o/p*)307) n-Propyl n-Pentyl n-Pentyl 2 o/p*) 308) iso-Propyl n-Pentyln-Pentyl 2 o/p*) 309) n-Butyl n-Pentyl n-Pentyl 2 o/p*) 310)2-Methylpropyl n-Pentyl n-Pentyl 2 o/p*) 311) 1-Methylpropyl n-Pentyln-Pentyl 2 o/p*) 312) 2,2-Dimethylpropyl n-Pentyl n-Pentyl 2 o/p*) 313)n-Pentyl n-Pentyl n-Pentyl 2 o/p*) 314) 3-Methylbutyl n-Pentyl n-Pentyl2 o/p*) 315) 2-Methylbutyl n-Pentyl n-Pentyl 2 o/p*) 316) 1-Methylbutyln-Pentyl n-Pentyl 2 o/p*) 317) n-Hexyl n-Pentyl n-Pentyl 2 o/p*) 318)n-Heptyl n-Pentyl n-Pentyl 2 o/p*) 319) n-Octyl n-Pentyl n-Pentyl 2o/p*) 320) 2-Ethylhexyl n-Pentyl n-Pentyl 2 o/p*) 321) Methyl n-Hexyln-Hexyl 2 o/p*) 322) Ethyl n-Hexyl n-Hexyl 2 o/p*) 323) n-Propyl n-Hexyln-Hexyl 2 o/p*) 324) iso-Propyl n-Hexyl n-Hexyl 2 o/p*) 325) n-Butyln-Hexyl n-Hexyl 2 o/p*) 326) 2-Methylpropyl n-Hexyl n-Hexyl 2 o/p*) 327)1-Methylpropyl n-Hexyl n-Hexyl 2 o/p*) 328) 2,2-Dimethylpropyl n-Hexyln-Hexyl 2 o/p*) 329) n-Pentyl n-Hexyl n-Hexyl 2 o/p*) 330) 3-Methylbutyln-Hexyl n-Hexyl 2 o/p*) 331) 2-Methylbutyl n-Hexyl n-Hexyl 2 o/p*) 332)1-Methylbutyl n-Hexyl n-Hexyl 2 o/p*) 333) n-Hexyl n-Hexyl n-Hexyl 2o/p*) 334) n-Heptyl n-Hexyl n-Hexyl 2 o/p*) 335) n-Octyl n-Hexyl n-Hexyl2 o/p*) 336) 2-Ethylhexyl n-Hexyl n-Hexyl 2 o/p*) 337) Methyl MethoxyMethoxy 2 o/p*) 338) Ethyl Methoxy Methoxy 2 o/p*) 339) n-Propyl MethoxyMethoxy 2 o/p*) 340) iso-Propyl Methoxy Methoxy 2 o/p*) 341) n-ButylMethoxy Methoxy 2 o/p*) 342) 2-Methylpropyl Methoxy Methoxy 2 o/p*) 343)1-Methylpropyl Methoxy Methoxy 2 o/p*) 344) 2,2-Dimethylpropyl MethoxyMethoxy 2 o/p*) 345) n-Pentyl Methoxy Methoxy 2 o/p*) 346) 3-MethylbutylMethoxy Methoxy 2 o/p*) 347) 2-Methylbutyl Methoxy Methoxy 2 o/p*) 348)1-Methylbutyl Methoxy Methoxy 2 o/p*) 349) n-Hexyl Methoxy Methoxy 2o/p*) 350) n-Heptyl Methoxy Methoxy 2 o/p*) 351) n-Octyl Methoxy Methoxy2 o/p*) 352) 2-Ethylhexyl Methoxy Methoxy 2 o/p*) 353) Methyl EthoxyEthoxy 2 o/p*) 354) Ethyl Ethoxy Ethoxy 2 o/p*) 355) n-Propyl EthoxyEthoxy 2 o/p*) 356) iso-Propyl Ethoxy Ethoxy 2 o/p*) 357) n-Butyl EthoxyEthoxy 2 o/p*) 358) 2-Methylpropyl Ethoxy Ethoxy 2 o/p*) 359)1-Methylpropyl Ethoxy Ethoxy 2 o/p*) 360) 2,2-Dimethylpropyl EthoxyEthoxy 2 o/p*) 361) n-Pentyl Ethoxy Ethoxy 2 o/p*) 362) 3-MethylbutylEthoxy Ethoxy 2 o/p*) 363) 2-Methylbutyl Ethoxy Ethoxy 2 o/p*) 364)1-Methylbutyl Ethoxy Ethoxy 2 o/p*) 365) n-Hexyl Ethoxy Ethoxy 2 o/p*)366) n-Heptyl Ethoxy Ethoxy 2 o/p*) 367) n-Octyl Ethoxy Ethoxy 2 o/p*)368) 2-Ethylhexyl Ethoxy Ethoxy 2 o/p*) *) o/p represents ortho- andpara-substituted

Example 4

Standardized Methods for Photostability Determination (Suntest)

A 5% by weight alcoholic solution of the sunscreen to be tested isapplied, using an Eppendorf pipette (20 μl), to the milled area on aglass plate. Owing to the presence of the alcohol, the solution isdistributed uniformly on the roughened glass surface. The amount appliedcorresponds to the amount of sunscreen required to obtain an average sunprotection factor in suncreams. In the test, 4 glass plates areirradiated each time. The evaporation time and the irradiation each lastfor 30 minutes. The glass plates are cooled slightly during theirradiation by a water cooling system located at the base of the Suntestapparatus. The temperature inside the Suntest apparatus during theirradiation is 40° C. After the samples have been irradiated, they arewashed with ethanol into a dark 50 ml graduated flask and measured in aphotometer. The blank samples are applied in the same way to glassplates and evaporated at room temperature for 30 minutes. Like the othersamples, they are washed off with ethanol and diluted to 100 ml andmeasured.

Photostability Comparative Tests:

General Method for Preparing Emulsions for Cosmetic Purposes

All the oil-soluble ingredients are heated to 85° C. in a stirredvessel. When all the ingredients have melted or are present as liquidphase, the aqueous phase is incorporated by homogenization. The emulsionis cooled to about 40° C. with stirring, is perfumed and homogenized,and is then cooled to 25° C. while stirring continuously.

Preparations

Mass content (% by weight) Example 5 Lip care composition ad 100eucerinum anhydricum 10.00  glycerol 10.00  titanium dioxide 5.00compound No. 1 in Table 2 8.00 octyl methoxycinnamate 5.00 zinc oxide4.00 castor oil 4.00 pentaerythrityl stearate/caprate/caprylate/adipate3.00 glyceryl stearate SE 2.00 beeswax 2.00 microcrystalline wax 2.00quaternium-18 bentonite 1.50 PEG-45/dodecyl glycol copolymer Example 6Lip care composition ad 100 eucerinum anhydricum 10.00  glycerol 10.00 titanium dioxide 5.00 compound No. 20 in Table 2 8.00 octylmethoxycinnamate 5.00 zinc oxide 4.00 castor oil 4.00 pentaerythritylstearate/caprate/caprylate/adipate 3.00 glyceryl stearate SE 2.00beeswax 2.00 microcrystalline wax 2.00 quaternium-18 bentonite 1.50PEG-45/dodecyl glycol copolymer Example 7 Sunblocker composition withmicropigments ad 100 water 10.00  octyl methoxycinnamate 6.00 PEG-7hydrogenated castor oil 6.00 titanium dioxide 5.00 compound No. 1 inTable 2 5.00 mineral oil 5.00 isoamyl p-methoxycinnamate 5.00 propyleneglycol 3.00 jojoba oil 3.00 4-methylbenzylidenecamphor 2.00PEG-45/dodecyl glycol copolymer 1.00 dimethicone 0.50 PEG-40hydrogenated castor oil 0.50 tocopheryl acetate 0.50 phenoxyethanol 0.20EDTA Example 8 Sunblocker composition with micropigments ad 100 water10.00  octyl methoxycinnamate 6.00 PEG-7 hydrogenated castor oil 6.00titanium dioxide 5.00 compound No. 20 in Table 2 5.00 mineral oil 5.00isoamyl p-methoxycinnamate 5.00 propylene glycol 3.00 jojoba oil 3.004-methylbenzylidenecamphor 2.00 PEG-45/dodecyl glycol copolymer 1.00dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50 tocopheryl acetate0.50 phenoxyethanol 0.20 EDTA Example 9 Non-greasy gel ad 100 water 8.00octyl methoxycinnamate 7.00 titanium dioxide 5.00 compound No. 1 inTable 2 5.00 glycerol 5.00 PEG-25 PABA 1.00 4-methylbenzylidenecamphor0.40 acrylate C10-C30 alkyl acrylate crosspolymer 0.30imidazolidinylurea 0.25 hydroxyethylcellulose 0.25 sodium methylparaben0.20 disodium EDTA 0.15 fragrance 0.15 sodium propylparaben 0.10 sodiumhydroxide Example 10 Non-greasy gel ad 100 water 8.00 octylmethoxycinnamate 7.00 titanium dioxide 5.00 compound No. 20 in Table 25.00 glycerol 5.00 PEG-25 PABA 1.00 4-methylbenzylidenecamphor 0.40acrylate C10-C30 alkyl acrylate crosspolymer 0.30 imidazolidinylurea0.25 hydroxyethylcellulose 0.25 sodium methylparaben 0.20 disodium EDTA0.15 fragrance 0.15 sodium propylparaben 0.10 sodium hydroxide Example11 Suncream (SPF 20) ad 100 water 8.00 octylmethoxycinnamate 8.00titanium dioxide 6.00 PEG-7 hydrogenated castor oil 5.00 compound No. 1in Table 2 6.00 mineral oil 5.00 zinc oxide 5.00 isopropyl palmitate5.00 imidazolidinylurea 3.00 jojoba oil 2.00 PEG-45/dodecyl glycolcopolymer 1.00 4-methylbenzylidenecamphor 0.60 magnesium stearate 0.50tocopheryl acetate 0.25 methylparaben 0.20 disodium EDTA 0.15propylparaben Example 12 Suncream (SPF 20) ad 100 water 8.00octylmethoxycinnamate 8.00 titanium dioxide 6.00 PEG-7 hydrogenatedcastor oil 5.00 compound No. 20 in Table 2 6.00 mineral oil 5.00 zincoxide 5.00 isopropyl palmitate 5.00 imidazolidinylurea 3.00 jojoba oil2.00 PEG-45/dodecyl glycol copolymer 1.00 4-methylbenzylidenecamphor0.60 magnesium stearate 0.50 tocopheryl acetate 0.25 methylparaben 0.20disodium EDTA 0.15 propylparaben Example 13 Water-resistant suncream ad100 water 8.00 octyl methoxycinnamate 5.00 PEG-7 hydrogenated castor oil5.00 propylene glycol 4.00 isopropyl palmitate 4.00 caprylic/caprictriglyceride 5.00 compound No. 1 in Table 2 4.00 glycerol 3.00 jojobaoil 2.00 4-methylbenzylidenecamphor 2.00 titanium dioxide 1.50PEG-45/dodecyl glycol copolymer 1.50 dimethicone 0.70 magnesium sulfate0.50 magnesium stearate 0.15 fragrance Example 14 Water-resistantsuncream ad 100 water 8.00 octyl methoxycinnamate 5.00 PEG-7hydrogenated castor oil 5.00 propylene glycol 4.00 isopropyl palmitate4.00 caprylic/capric triglyceride 5.00 compound No. 20 in Table 2 4.00glycerol 3.00 jojoba oil 2.00 4-methylbenzylidenecamphor 2.00 titaniumdioxide 1.50 PEG-45/dodecyl glycol copolymer 1.50 dimethicone 0.70magnesium sulfate 0.50 magnesium stearate 0.15 fragrance Example 15Sunmilk (SPF 6) ad 100 water 10.00  mineral oil 6.00 PEG-7 hydrogenatedcastor oil 5.00 isopropyl palmitate 3.50 octyl methoxycinnamate 5.00compound No. 1 in Table 2 3.00 caprylic/capric triglyceride 3.00 jojobaoil 2.00 PEG-45/dodecyl glycol copolymer

We claim:
 1. A 4,4-diarylbutadiene of the formula Ia,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings: R¹ and R² are hydrogen, or are selectedfrom the group consisting of C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl,C₃-C₁₀-cycloalkyl, C₃-C₁₀-cycloalkenyl, C₁-C₁₂-alkoxy,C₁-C₂₀-alkoxycarbonyl, C₁-C₁₂-alkylamino, C₁-C₁₂-dialkylamino, aryl,hetaryl, any of which may be unsubstituted or substituted, andsubstituents which confer solubility in water and are selected from thegroup consisting of carboxylate, sulfonate, and ammonium residues; R³ isCOOR⁵ or CONR⁵R⁶; R⁴ is COOR⁶ or CONR⁵R⁶; R⁵ and R⁶ are hydrogen, or areselected from the group consisting of C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl,C₃-C₁₀-cycloalkyl, C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl,C₇-C₁₀-bicycloalkenyl, aryl, and hetaryl, any of which may beunsubstituted or substituted; n is 1 to 3 where R³ and R⁴ are not COOCH₃when R¹ and R² are hydrogen.
 2. A 4,4-diarylbutadiene of the formula Ib,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings: R¹ and R² are hydrogen, C₁-C₂₀-alkyl,C₁-C₁₂-alkoxy, or C₁-C₂₀-alkoxycarbonyl; R³ is COOR⁵ or CONR⁵R⁶; R⁴ isCOOR⁶ or CONR⁵R⁶; R⁵ and R⁶ are hydrogen, or are selected from the groupconsisting of C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,and hetaryl, any of which may be unsubstituted or substituted; where R³and R⁴ are not COOCH₃ when R¹ and R² are hydrogen.
 3. A4,4-diarylbutadiene of the formula Ic,

where the diene system has the Z,Z; Z,E; E,Z or E,E configuration or amixture thereof, and where the variables independently of one anotherhave the following meanings: R¹ and R² are hydrogen, C₁-C₂₀-alkyl,C₁-C₁₂-alkoxy, or C₁-C₂₀-alkoxycarbonyl; R³ is COOR⁵ or CONR⁵R⁶; R⁴ isCOOR⁶ or CONR⁵R⁶; R⁵ and R⁶ are hydrogen, or are selected from the groupconsisting of C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-cycloalkyl,C₇-C₁₀-bicycloalkyl, C₃-C₁₀-cycloalkenyl, C₇-C₁₀-bicycloalkenyl, aryl,and hetaryl, any of which may be unsubstituted or substituted; where R³and R⁴ are not COOCH₃ when R¹ and R² are hydrogen.